CN110790515B - Transparent super-hydrophilic material with graphite phase carbon nitride and preparation method and application thereof - Google Patents
Transparent super-hydrophilic material with graphite phase carbon nitride and preparation method and application thereof Download PDFInfo
- Publication number
- CN110790515B CN110790515B CN201910993981.7A CN201910993981A CN110790515B CN 110790515 B CN110790515 B CN 110790515B CN 201910993981 A CN201910993981 A CN 201910993981A CN 110790515 B CN110790515 B CN 110790515B
- Authority
- CN
- China
- Prior art keywords
- graphite
- carbon nitride
- phase carbon
- transparent
- super
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/225—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/4505—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application
- C04B41/4529—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements characterised by the method of application applied from the gas phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5062—Borides, Nitrides or Silicides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/75—Hydrophilic and oleophilic coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
Abstract
The invention discloses a transparent super-hydrophilic material with graphite-phase carbon nitride and a preparation method and application thereof, wherein the transparent super-hydrophilic material with graphite-phase carbon nitride consists of a transparent substrate and a graphite-phase carbon nitride film evaporated on the transparent substrate, and the graphite-phase carbon nitride is calcined by a carbon nitride precursor; the preparation method comprises the steps of firstly, calcining the carbon-rich nitrogen compound serving as a raw material to prepare graphite-phase carbon nitride, and further evaporating the graphite-phase carbon nitride onto a substrate by a one-step vapor deposition method to obtain the transparent material with the super-hydrophilic property. The super-hydrophilic transparent material disclosed by the invention has super-hydrophilicity and super-lipophilicity, has good transmittance, does not influence visibility, has good thermal stability and acid and alkali corrosion resistance, and can be used for preparing self-cleaning materials, underwater oleophobic materials, antifogging materials, antibacterial materials and the like.
Description
Technical Field
The invention belongs to the technical field of super-hydrophilic materials, and relates to a transparent super-hydrophilic material with graphite-phase carbon nitride, a preparation method of the transparent super-hydrophilic material and application of the transparent super-hydrophilic material.
Background
At present, glass walls and mirrors become common transparent materials for buildings and decorations, but due to weather and environment reasons, the visibility and transparency of the glass walls can be influenced by the adhesion of dust and haze, condensation of water vapor, fog and the like. In order to solve the problem, researchers provide a super-hydrophilic coating with good wettability, the acting force of the super-hydrophilic coating on water drops is larger than the surface tension of the water drops, so that the water drops are uniformly spread, and the pollutants can be self-cleaned under the action of external force such as wind power or gravity while the anti-fog effect is achieved.
Jiang et al, which uses ammonium metavanadate, butyl titanate, TEOS, acetylacetone and the like as main raw materials, and adopts a pulling method to prepare a composite film, show good super-hydrophilic performance under sunlight irradiation. However, many preparation methods similar to the above composite films still rely on toxic reagents and are cumbersome in steps and poor in reproducibility; the prepared material has poor performances in the aspects of chemical corrosion resistance, temperature resistance and the like, shows poor stability, and loses super-hydrophilicity under the action of certain acid-base corrosion and external force.
The carbon nitride has a mild band gap of 2.7-2.8 eV and a visible light absorption band of about 450-460 nm; and the graphite phase carbon nitride has stable property, is not dissolved in acid, alkali or organic solvent, becomes a firm material under the environmental condition, has better chemical and thermodynamic stability, and has low price and simple preparation. At present, graphite-phase carbon nitride is mainly used in the aspects of photocatalysis, hydrogen storage materials, capacitance materials and the like, and no relevant report of preparing an ultra-hydrophilic transparent material by using carbon nitride as a raw material exists.
Disclosure of Invention
The invention aims to provide a transparent super-hydrophilic material with graphite-phase carbon nitride and a preparation method thereof aiming at overcoming the defects of the prior art.
Another object of the present invention is to provide the use of the above transparent superhydrophilic material.
The transparent super-hydrophilic material with graphite-phase carbon nitride is composed of a transparent base material and a graphite-phase carbon nitride film evaporated on the transparent base material, wherein the graphite-phase carbon nitride is formed by calcining a carbon nitride precursor.
The graphite phase carbon nitride has high adsorption energy, and the formed film has strong attraction to super-lyophilic liquid (such as aqueous phase solution, organic phase solution and the like) to further form a super-hydrophilic interface, so that the material not only has good super-hydrophilicity, but also has good super-lipophilicity, and is a double super-hydrophilic material. In addition, due to the excellent properties of the graphite-phase carbon nitride, the transparent super-hydrophilic material with the graphite-phase carbon nitride also has excellent temperature resistance and acid-base corrosion resistance, so that the performance of the transparent super-hydrophilic material is improved.
The preparation method of the transparent super-hydrophilic material with graphite-phase carbon nitride provided by the invention comprises the following steps:
(1) calcining the carbon-nitrogen compound precursor at 450-600 ℃ for 1-4 h to prepare graphite-phase carbon nitride;
(2) and (3) placing the substrate which is rinsed by the solvent above the graphite-phase carbon nitride, and then evaporating for 1-4 h at 450-550 ℃.
The step (1) of the preparation method of the transparent super-hydrophilic material with graphite-phase carbon nitride aims to obtain the graphite-phase carbon nitride. The precursor of the carbon-nitrogen compound is rich carbon-nitrogen compound such as urea, thiourea or melamine. Before calcination, the precursor of the carbon-nitrogen compound is heated to 450-600 ℃ at a heating rate of not higher than 10 ℃/min, so that the polymerization degree of the product is better, and the obtained substance is purer. In the invention, the heating rate of the carbon-nitrogen compound precursor before calcination is 5-10 ℃/min.
The preparation method of the transparent super-hydrophilic material with graphite-phase carbon nitride comprises the step (2) of evaporating a layer of graphite-phase carbon nitride film on the surface of a transparent substrate by an evaporation method. In order to obtain a graphite-phase carbon nitride thin film having super-hydrophilicity, it is necessary to rinse a substrate and strictly control the deposition conditions.
The transparent substrate is a transparent material which can endure a temperature of 300 ℃ or more, such as glass, transparent ceramic, and the like. Carry out the rinse to transparent substrate surface, can guarantee transparent substrate surface cleanness on the one hand, on the other hand helps graphite phase carbon nitride to construct micro-nano structure, and the stability of super hydrophilic effect of increase that micro-nano structure constructed can be better. The rinsing method adopted by the invention is that the base material is placed in a container filled with solvent for ultrasonic rinsing for 10-30 min, and then dried below 100 ℃ for standby. The solvent is ethanol, water, acetone, hydrochloric acid, hydrogen fluoride or ammonium fluoride.
The substrate needs to be placed horizontally on the graphite phase carbon nitride to ensure uniform evaporation. The distance between the substrate and the graphite phase carbon nitride is at least 1cm, so that the vapor deposition process is ensured.
Before evaporation, the temperature of the graphite-phase carbon nitride is increased to 450-550 ℃ at a temperature rise rate of not more than 5 ℃/min, so that the graphite-phase carbon nitride is completely gasified and uniformly spread on the transparent substrate. In the invention, the heating rate before the evaporation of the graphite-phase carbon nitride is 2-5 ℃/min.
In the evaporation process, the air velocity around the graphite-phase carbon nitride needs to be controlled so that the carbon nitride can be evaporated on the transparent substrate as much as possible, and the waste of the graphite-phase carbon nitride is avoided. In the invention, carbon nitride is placed in an evaporation container, a transparent substrate is placed at least 1cm above the carbon nitride, and then the carbon nitride and the transparent substrate are integrally placed in a closed or semi-closed environment, so that the airflow around the graphite-phase carbon nitride is effectively controlled. By the mode, the dosage of the graphite phase carbon nitride is measured according to that the dosage of the graphite phase carbon nitride is more than or equal to 0.004g of graphite phase carbon nitride per square centimeter of the transparent base material.
After the evaporation is finished, the evaporation material is cooled to be below 100 ℃, and then the evaporation material is taken out, so that the gasified graphite-phase carbon nitride is favorably deposited on the transparent substrate, and the transparent super-hydrophilic material is favorably obtained.
The transparent super-hydrophilic material with graphite-phase carbon nitride provided by the invention can be used for preparing self-cleaning materials, underwater oleophobic materials, antifogging materials, antibacterial materials and the like.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the method, the carbon-nitrogen-rich compound is used as a raw material, the graphite-phase carbon nitride is prepared through calcination, and then the graphite-phase carbon nitride is evaporated on the transparent substrate through a one-step vapor deposition method, so that the transparent super-hydrophilic material with the graphite-phase carbon nitride is obtained.
2. The method has the advantages of low cost of the adopted raw materials, simple operation of the preparation method, contribution to industrial production and convenience for popularization in the field.
3. The transparent super-hydrophilic material with graphite-phase carbon nitride provided by the invention has super-hydrophilicity, super-lipophilicity, good transmittance, good temperature resistance and acid-base corrosion resistance, and is used as a high-quality material for buildings and ornaments.
4. The transparent super-hydrophilic material with graphite-phase carbon nitride provided by the invention can be used for preparing self-cleaning materials, underwater oleophobic materials, antifogging materials, antibacterial materials and the like.
Drawings
FIG. 1 is an electron micrograph of graphite-phase carbonitride prepared in example 3 of the present invention.
Fig. 2 is an XRD pattern of graphite-phase carbon nitride prepared in example 3 of the present invention.
FIG. 3 is an electron microscope image of the surface of transparent super-hydrophilic glass with graphite-phase carbon nitride prepared in example 3 of the present invention.
FIG. 4 is a cross-sectional electron microscope image of transparent super-hydrophilic glass with graphite-phase carbon nitride prepared in example 3 of the present invention.
FIG. 5 is a graph showing the water contact angle test of the surface of transparent super-hydrophilic glass with graphite-phase carbon nitride prepared in example 3 of the present invention.
Fig. 6 is a schematic diagram of the super-hydrophilic effect of the transparent super-hydrophilic glass with graphite-phase carbon nitride prepared in embodiment 3 of the present invention.
FIG. 7 is a graph showing the contact angle of methyl oleate with graphite phase carbon nitride on the surface of transparent super-hydrophilic glass prepared in example 3 of the present invention.
FIG. 8 is a cyclohexane contact angle test chart of the surface of transparent super-hydrophilic glass with graphite-phase carbon nitride prepared in example 3 of the present invention.
Fig. 9 is a graph showing the acid and alkali resistance of the transparent super-hydrophilic glass with graphite phase carbon nitride prepared in example 3 of the present invention.
FIG. 10 is a graph showing the temperature resistance of the transparent super-hydrophilic glass with graphite-phase carbon nitride prepared in example 3 of the present invention.
FIG. 11 is a self-cleaning diagram of a transparent super-hydrophilic glass with graphite-phase carbon nitride prepared in example 3 of the present invention.
FIG. 12 is a graph of transparent ultrahydrophilic glass underwater oleophobic with graphite-phase carbon nitride prepared in example 3 of the invention.
FIG. 13 is an anti-fog pattern of transparent ultraphilic glass with graphite-phase carbon nitride prepared in example 3 of the present invention.
Fig. 14 is a bacteriostatic graph, in which (a) is a substrate (base) glass bacteriostatic graph in example 3 of the present invention, and (b) is a transparent super-hydrophilic glass bacteriostatic graph with graphite-phase carbon nitride prepared in example 3 of the present invention.
Detailed Description
The technical solutions of the present invention are described in detail below with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the amount of graphite-phase carbon nitride used was measured on one side of the evaporated transparent substrate.
Example 1
In this example, urea is used as a precursor, and 2cm by 2.5cm silicate glass (sailboat brand, No.7101) is used as a base material to prepare the transparent super-hydrophilic material, which includes the following steps:
(1) preparation of graphite phase carbon nitride
Heating 10g of urea to 450 ℃ at the heating rate of 5 ℃/min, and calcining for 4h at the temperature to obtain graphite-phase carbon nitride;
(2) the substrate is placed in ethanol for ultrasonic rinsing for 10min, the rinsed substrate is placed above an evaporation plating porcelain boat which is uniformly paved with 0.02g of graphite phase carbon nitride after being dried, the distance between the substrate and the surface of the graphite phase carbon nitride is about 1.5cm, the substrate and the surface of the graphite phase carbon nitride are integrally placed in an evaporation plating machine, then the temperature is increased to 450 ℃ at the rate of 2 ℃/min, evaporation plating is carried out for 4h at the temperature, and the substrate is cooled to below 100 ℃ along with a furnace after the evaporation plating is finished, so that the transparent super-hydrophilic material is obtained.
Example 2
In this embodiment, a transparent super-hydrophilic material is prepared by using urea as a precursor and quartz glass of 2cm × 2.5cm as a substrate, and the steps are as follows:
(1) preparation of graphite phase carbon nitride
Heating 10g of urea to 500 ℃ at the heating rate of 5 ℃/min, and calcining for 2h at the temperature to obtain graphite-phase carbon nitride;
(2) putting a substrate into acetone, ultrasonically rinsing for 10min, drying the rinsed substrate, putting the substrate above an evaporation plating porcelain boat uniformly covered with 0.05g of graphite-phase carbon nitride, wherein the distance between the substrate and the surface of the graphite-phase carbon nitride is about 1.5cm, putting the substrate and the surface of the graphite-phase carbon nitride into an evaporation plating machine, heating to 500 ℃ at the heating rate of 2 ℃/min, evaporating for 2h at the temperature, and cooling to below 100 ℃ along with a furnace after the evaporation plating is finished to obtain the transparent super-hydrophilic material.
Example 3
In this example, urea is used as a precursor, and 2cm × 2.5cm silicate glass (sailboat brand, No.7101) is used as a base material to prepare the transparent super-hydrophilic material, which includes the following steps:
(1) preparation of graphite phase carbon nitride
Heating 20g of urea to 550 ℃ at the heating rate of 5 ℃/min, and calcining for 3h at the temperature to obtain graphite-phase carbon nitride;
(2) placing the substrate in ethanol for ultrasonic rinsing for 20min, drying the rinsed substrate, placing the rinsed substrate above an evaporation plating porcelain boat uniformly covered with 0.2g of graphite-phase carbon nitride, wherein the distance between the substrate and the surface of the graphite-phase carbon nitride is about 1.5cm, placing the substrate and the surface of the graphite-phase carbon nitride into an evaporation plating machine, heating to 550 ℃ at the heating rate of 5 ℃/min, evaporating for 4h at the temperature, and cooling to below 100 ℃ along with a furnace after the evaporation plating is finished to obtain the transparent super-hydrophilic material.
Example 4
In this embodiment, a transparent super-hydrophilic material is prepared by using urea as a precursor and using 2.5cm × 2.5cm transparent magnesia ceramic as a substrate, and the steps are as follows:
(1) preparation of graphite phase carbon nitride
Heating 20g of urea to 550 ℃ at the heating rate of 5 ℃/min, and calcining for 2h at the temperature to obtain graphite-phase carbon nitride;
(2) placing the substrate in 36% hydrochloric acid solution, ultrasonically rinsing for 20min, drying the rinsed substrate, placing the dried substrate above an evaporation porcelain boat uniformly covered with 0.2g of graphite-phase carbon nitride, wherein the distance between the substrate and the surface of the graphite-phase carbon nitride is about 1.5cm, placing the substrate and the surface of the graphite-phase carbon nitride into an evaporation machine, heating to 550 ℃ at the heating rate of 5 ℃/min, evaporating for 1h at the temperature, and cooling to below 100 ℃ along with the furnace after the evaporation is finished to obtain the transparent super-hydrophilic material.
Example 5
In this embodiment, melamine is used as a precursor, and soda-lime glass of 1cm × 2cm is used as a substrate to prepare the transparent super-hydrophilic material, and the steps are as follows:
(1) preparation of graphite phase carbon nitride
Heating 8g of melamine to 520 ℃ at a heating rate of 5 ℃/min, and calcining for 2h at the temperature to obtain graphite-phase carbon nitride;
(2) putting a substrate in 5mol/L ammonium fluoride solution, ultrasonically rinsing for 30min, drying the rinsed substrate, putting the substrate above an evaporation plating porcelain boat uniformly paved with 0.05g of graphite-phase carbon nitride, wherein the distance between the substrate and the surface of the graphite-phase carbon nitride is about 1cm, putting the substrate and the graphite-phase carbon nitride into an evaporation plating machine, heating to 500 ℃ at the heating rate of 2 ℃/min, evaporating for 2h at the temperature, and cooling to below 100 ℃ along with the furnace after the evaporation plating is finished to obtain the transparent super-hydrophilic material.
Example 6
In this embodiment, a transparent superhydrophilic material is prepared by using melamine as a precursor and 1cm × 2cm transparent alumina ceramic as a substrate, and the steps are as follows:
(1) preparation of graphite phase carbon nitride
Heating 10g of melamine to 520 ℃ at the heating rate of 8 ℃/min, and calcining for 2h at the temperature to obtain graphite-phase carbon nitride;
(2) putting a substrate in a hydrogen fluoride solution with the concentration of 5mol/L for ultrasonic rinsing for 10min, drying the rinsed substrate, putting the substrate above an evaporation plating porcelain boat uniformly paved with 0.05g of graphite-phase carbon nitride, wherein the distance between the substrate and the surface of the graphite-phase carbon nitride is about 2cm, putting the substrate and the graphite-phase carbon nitride into an evaporation plating machine, heating to 550 ℃ at the heating rate of 3 ℃/min, evaporating for 1h at the temperature, and cooling to below 100 ℃ along with the furnace after the evaporation plating is finished to obtain the transparent super-hydrophilic material.
Example 7
In this example, melamine is used as a precursor, and 5cm × 2cm silicate glass (sailboat brand, No.7101) is used as a substrate to prepare the transparent super-hydrophilic material, which includes the following steps:
(1) preparation of graphite phase carbon nitride
Heating 15g of melamine to 600 ℃ at the heating rate of 10 ℃/min, and calcining for 1h at the temperature to obtain graphite-phase carbon nitride;
(2) placing the substrate in water for ultrasonic rinsing for 10min, drying the rinsed substrate, placing the rinsed substrate above an evaporation porcelain boat uniformly covered with 0.11g of graphite-phase carbon nitride, wherein the distance between the substrate and the surface of the graphite-phase carbon nitride is about 2cm, placing the substrate and the surface of the graphite-phase carbon nitride in a closed environment, heating to 550 ℃ at the heating rate of 2 ℃/min, evaporating for 1h at the temperature, and cooling to below 100 ℃ along with a furnace after the evaporation is finished to obtain the transparent super-hydrophilic material.
The structural characteristics, ultra-hydrophilicity, temperature resistance, acid and alkali corrosion resistance, and bacterial inhibition of some examples are explained in detail below.
1. Structural features
The graphite-phase carbon nitride prepared in step (1) of example 3 was analyzed by sem, and the results are shown in fig. 1, and it can be seen from fig. 1 that the prepared graphite-phase carbon nitride has typical characteristics of graphite-phase carbon nitride, exhibits a lamellar structure and a partial curl, and has a larger specific surface area than a bulk structure.
The X-ray diffraction test analysis of the graphite-phase carbon nitride prepared in step (1) of example 3 showed that the test results are shown in fig. 2, and it can be seen from fig. 2 that characteristic peaks of graphite-phase carbon nitride appeared at about 13 ° and 27 °, indicating that pure graphite-phase carbon nitride was prepared.
The transparent super-hydrophilic glass prepared in example 3 was analyzed by scanning electron microscopy, and the results are shown in fig. 3, and it can be seen from fig. 3 that a layer of graphite-phase carbon nitride was uniformly spread on the surface of the substrate in the form of a lamellar sheet.
The transparent super-hydrophilic glass prepared in example 3 was analyzed by cross-sectional scanning electron microscopy, and the results are shown in fig. 4. as can be seen from fig. 4, a graphite-phase carbon nitride thin film having a thickness of approximately 3 μm was formed on the substrate surface.
2. Super-affinity analysis
(1) Super hydrophilic property
The contact angle test analysis of the transparent super-hydrophilic glass prepared in example 3 is performed, and the test result is shown in fig. 5, and it can be seen from fig. 5 that the surface contact angle is 0 °, and the super-hydrophilic effect is achieved.
The transparent super-hydrophilic glass prepared in example 3 was dropped on water, and the collected picture is shown in fig. 6, and it can be seen from fig. 6 that the prepared transparent super-hydrophilic glass has excellent hydrophilicity and transparency.
(2) Super lipophilicity
Methyl oleate CA test analysis is carried out on the transparent super-hydrophilic glass prepared in example 3, the test result is shown in figure 7, and as can be seen from figure 7, the contact angle of the methyl oleate liquid drop is less than 5 degrees, and the effect of super-hydrophilic methyl oleate is achieved.
The transparent super-hydrophilic glass prepared in example 3 was analyzed by cyclohexane CA test, and the test results are shown in fig. 8, and it can be seen from fig. 8 that the contact angle of cyclohexane drops is less than 5 °, which achieves the effect of super-hydrophilic cyclohexane.
The contact angles of the conventional hydrophilic and lipophilic materials are not uniform in the range below 90 degrees, and the overall spreading effect of the materials is inconsistent. The transparent super-hydrophilic material with graphite-phase carbon nitride provided by the invention can completely control the contact angle of water and oil to be below 5 degrees, has better spreading effect, high spreading speed, large and uniform spreading area, and thin formed liquid film, thereby having less influence on the visibility of the transparent material, and being beneficial to the uniformity of industrial falling film and the like.
3. Acid and alkali resistance
The transparent super-hydrophilic glass prepared in the example 3 is respectively placed in aqueous solutions (the pH values of the aqueous solutions are adjusted by hydrochloric acid and sodium hydroxide) with the pH values of 1, 5, 7, 9, 11 and 15, then the super-hydrophilic glass is soaked in the aqueous solutions, taken out and dried, the contact angles of the super-hydrophilic glass are measured by water drops, the contact angles corresponding to different pH values obtained by measurement are shown in a figure 9, and as can be seen from the figure 9, the prepared super-hydrophilic transparent glass has good stability between the pH values of 5 and 9, and can be suitable for most conventional environments at present.
4. Temperature resistance
The transparent super-hydrophilic glass prepared in example 3 was placed at-225 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃, 450 ℃, 550 ℃, and 600 ℃ respectively, and then placed for 1min, and then returned to normal temperature, and then the contact angle was measured with a water drop, and the measured contact angles at different temperatures were as shown in fig. 10, and it can be seen from fig. 10 that the contact angle of the attachment on the prepared transparent super-hydrophilic glass does not substantially change with temperature, and the surface has excellent temperature resistance.
Application example 1
Firstly, some 80-mesh sand grains are uniformly scattered on the transparent super-hydrophilic glass prepared in the example 3, then water drops are dripped on the top of the transparent super-hydrophilic glass, the picture acquired in the water drop spreading process is shown in fig. 11, and as can be seen from fig. 11, nothing is completely attached to the place where the water is spread, because the adhesive force of the super-hydrophilic surface to the water is stronger than that of the sand grains, the water drops take away the sand grains by utilizing the self gravity.
Application example 2
The transparent super-hydrophilic glass prepared in the embodiment 3 is placed in a container filled with water, the transparent super-hydrophilic glass is completely covered by the water, then a plurality of drops of dyed carbon tetrachloride heavy oil are dripped on the surface of the transparent super-hydrophilic glass by using an injector, pictures collected in the dripping process are shown in figure 12, and as can be seen from figure 12, the transparent super-hydrophilic glass has excellent oleophobic property underwater, the transparent super-hydrophilic glass can be used for underwater oil transportation, and the change of the oleophobic property of the super-hydrophilic glass material can be observed in time in the using process, so that the super-hydrophilic glass can be replaced in time. In addition, the super-hydrophilic glass can be used for observing the oil-water separation effect in actual production, thereby being beneficial to the analysis of oil-water separation influencing factors.
Application example 3
A piece of silicate glass (sailing boat brand, NO.7101) and the transparent super-hydrophilic glass prepared in the example 3 are respectively fumigated by water mist at the temperature of 80 ℃, pictures collected after the fumigation process are shown in figure 13, and it can be seen from figure 13 that the common transparent glass does not have antifogging property, while the transparent super-hydrophilic glass prepared in the example 3 has good antifogging property, because fog drops in the air can be spread on the super-hydrophilic surface quickly and cannot be condensed into liquid drops to influence the sight, the transparent super-hydrophilic glass can be used for glass curtain walls and windows.
Application example 4
A piece of silicate glass (sailing boat brand, NO.7101) and the transparent super-hydrophilic glass prepared in example 3 are respectively placed in a culture medium of escherichia coli (according to the conditions that 1g/L of protein nitrogen, 3g/L of beef extract, 5g/L of sodium chloride and 30g/L of agar powder are added into 50mL of deionized water to be uniformly mixed, a solid culture medium is obtained after cooling, 5 mul of escherichia coli solution is placed in the center of the culture medium to be cultured), pictures collected after being placed for 3 days under the illumination condition of an LED lamp are shown in figure 14, from (a) in figure 14, the common glass has no bacteriostatic property, from (b) in figure 14, the transparent super-hydrophilic glass prepared in example 3 has good bacteriostatic property, because graphite phase carbon is a photocatalyst, the oxidation ability of generating free radicals under the illumination condition can inhibit bacteria, the evaporated super-hydrophilic glass still has the effect, and the transparent super-hydrophilic glass can be used in a humid environment, an antibacterial window and the like.
Claims (7)
1. A preparation method of a transparent super-hydrophilic material with graphite-phase carbon nitride is characterized by comprising the following steps:
(1) calcining the carbon-nitrogen compound precursor at 450-600 ℃ for 1-4 h to obtain graphite-phase carbon nitride; heating the carbon-nitrogen compound precursor to 450-600 ℃, wherein the heating rate is not higher than 10 ℃/min;
(2) and (3) placing the transparent substrate which is washed by the solvent above the graphite-phase carbon nitride, wherein the distance between the transparent substrate and the graphite-phase carbon nitride is at least 1cm, and then evaporating at 450-550 ℃ for 1-4 h to obtain the transparent super-hydrophilic material with the graphite-phase carbon nitride.
2. The method for preparing the transparent super-hydrophilic material with graphite-phase carbon nitride according to claim 1, wherein in the step (1), the carbon nitride precursor is urea, thiourea or melamine.
3. The process for the preparation of a transparent superhydrophilic material having graphite phase carbon nitride according to claim 1 or 2, characterized in that the amount of graphite phase carbon nitride is measured as not less than 0.004g of graphite phase carbon nitride per square centimeter of transparent substrate.
4. The method for producing a transparent superhydrophilic material having graphite-phase carbon nitride according to claim 1 or 2, characterized in that in the step (2), the transparent substrate is a transparent material resistant to a temperature of 300 ℃ or higher; the solvent is ethanol, water, acetone, hydrochloric acid, hydrogen fluoride or ammonium fluoride.
5. The method for preparing a transparent super-hydrophilic material having graphite-phase carbon nitride according to claim 3, wherein in the step (2), the transparent substrate is a transparent material which can withstand a temperature of 300 ℃ or higher; the solvent is ethanol, water, acetone, hydrochloric acid, hydrogen fluoride or ammonium fluoride.
6. The method for preparing a transparent super-hydrophilic material with graphite-phase carbon nitride according to claim 3, wherein in the step (2), the temperature of the graphite-phase carbon nitride is raised to 450-550 ℃ at a rate of not higher than 5 ℃/min.
7. Use of the transparent super-hydrophilic material with graphite-phase carbon nitride prepared by the method of any one of claims 1 to 6 in the preparation of self-cleaning materials, underwater oleophobic materials, antifogging materials and bacteriostatic materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910993981.7A CN110790515B (en) | 2019-10-18 | 2019-10-18 | Transparent super-hydrophilic material with graphite phase carbon nitride and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910993981.7A CN110790515B (en) | 2019-10-18 | 2019-10-18 | Transparent super-hydrophilic material with graphite phase carbon nitride and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110790515A CN110790515A (en) | 2020-02-14 |
| CN110790515B true CN110790515B (en) | 2020-12-15 |
Family
ID=69439450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910993981.7A Active CN110790515B (en) | 2019-10-18 | 2019-10-18 | Transparent super-hydrophilic material with graphite phase carbon nitride and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110790515B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679108A (en) * | 2020-11-06 | 2021-04-20 | 汕头大学 | Photocatalytic self-cleaning glass and preparation method thereof |
| CN112608779B (en) * | 2020-12-28 | 2022-06-07 | 四川大学 | Lubricating grease based on carbonitride and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755383A (en) * | 2014-01-24 | 2014-04-30 | 福建农林大学 | Functional stone slab immobilized with graphite phase carbon nitride and preparation method of functional stone slab |
| CN105331949A (en) * | 2015-11-12 | 2016-02-17 | 西南交通大学 | Method for preparing carbon nitride film |
| CN105925954A (en) * | 2016-05-27 | 2016-09-07 | 清华大学 | Preparation method of semiconductor carbon nitride films |
| CN106206773A (en) * | 2016-08-16 | 2016-12-07 | 华中科技大学 | A kind of preparation method of graphite phase carbon nitride film modified electrod |
| CN106752446A (en) * | 2016-12-16 | 2017-05-31 | 国网山东省电力公司电力科学研究院 | A kind of modified automatically cleaning heat conduction fluorine carbon finishing paint of graphite phase carbon nitride graphene complex |
| CN107252701A (en) * | 2017-07-12 | 2017-10-17 | 西华师范大学 | A kind of high activity graphite phase carbon nitride material and preparation method thereof |
| CN109420516A (en) * | 2017-08-28 | 2019-03-05 | 广州中国科学院沈阳自动化研究所分所 | A kind of carbon nitride films of loading platinum and the preparation method and application thereof |
| CN109806769A (en) * | 2017-11-21 | 2019-05-28 | 天津淼宇科技发展有限公司 | Preparation method of modified graphite-phase carbon nitride material nanofiltration membrane |
| CN109850858A (en) * | 2019-03-22 | 2019-06-07 | 张家港市东大工业技术研究院 | A kind of synthetic method of hydrophily graphite phase carbon nitride material |
| US20190275559A1 (en) * | 2018-03-06 | 2019-09-12 | Indian Institute Of Technology Delhi | Formation of thin film like assembly by solvent non-evaporative method using centrifuge |
-
2019
- 2019-10-18 CN CN201910993981.7A patent/CN110790515B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755383A (en) * | 2014-01-24 | 2014-04-30 | 福建农林大学 | Functional stone slab immobilized with graphite phase carbon nitride and preparation method of functional stone slab |
| CN105331949A (en) * | 2015-11-12 | 2016-02-17 | 西南交通大学 | Method for preparing carbon nitride film |
| CN105925954A (en) * | 2016-05-27 | 2016-09-07 | 清华大学 | Preparation method of semiconductor carbon nitride films |
| CN106206773A (en) * | 2016-08-16 | 2016-12-07 | 华中科技大学 | A kind of preparation method of graphite phase carbon nitride film modified electrod |
| CN106752446A (en) * | 2016-12-16 | 2017-05-31 | 国网山东省电力公司电力科学研究院 | A kind of modified automatically cleaning heat conduction fluorine carbon finishing paint of graphite phase carbon nitride graphene complex |
| CN107252701A (en) * | 2017-07-12 | 2017-10-17 | 西华师范大学 | A kind of high activity graphite phase carbon nitride material and preparation method thereof |
| CN109420516A (en) * | 2017-08-28 | 2019-03-05 | 广州中国科学院沈阳自动化研究所分所 | A kind of carbon nitride films of loading platinum and the preparation method and application thereof |
| CN109806769A (en) * | 2017-11-21 | 2019-05-28 | 天津淼宇科技发展有限公司 | Preparation method of modified graphite-phase carbon nitride material nanofiltration membrane |
| US20190275559A1 (en) * | 2018-03-06 | 2019-09-12 | Indian Institute Of Technology Delhi | Formation of thin film like assembly by solvent non-evaporative method using centrifuge |
| CN109850858A (en) * | 2019-03-22 | 2019-06-07 | 张家港市东大工业技术研究院 | A kind of synthetic method of hydrophily graphite phase carbon nitride material |
Non-Patent Citations (1)
| Title |
|---|
| 光催化降解水体有机污染物的研究进展;周锋等;《材料工程》;20181031;第46卷(第10期);第10页第1栏第1段，第11页第1栏最后一段至第2栏第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110790515A (en) | 2020-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110790515B (en) | Transparent super-hydrophilic material with graphite phase carbon nitride and preparation method and application thereof | |
| CN101794670B (en) | Preparation method of photo anode of dye-sensitized solar cell with optical gradient | |
| Reddy et al. | Investigations on SnS films deposited by spray pyrolysis | |
| Mardare et al. | Undoped and Cr-doped TiO2 thin films obtained by spray pyrolysis | |
| CN109487245B (en) | Preparation method of super-hydrophobic hydrated alumina film | |
| Pal et al. | Spectrally selective absorber coating from transition metal complex for efficient photothermal conversion | |
| US20200399170A1 (en) | Coated glass sheet and method for producing same | |
| CN104745019A (en) | Preparation method for nano SiO2/TiO2 modified PVDF (polyvinylidene fluoride) super-hydrophobic composite film with self-cleaning characteristics | |
| CN110980664A (en) | Porous few-layer h-BN nanosheet and preparation method thereof | |
| CN111057998A (en) | Super-hydrophilic anti-fog coating and preparation method and application thereof | |
| CN101265034A (en) | Sulfur doping titanium dioxide thin film and preparation method thereof | |
| CN102491405A (en) | Composite nano-zinc oxide material and its preparation method | |
| US20130142995A1 (en) | Method for improving hydrophilicity of a coating film through treatment on a surface morphology and super-hydrophilic glass coating layer produced by the same | |
| Imai et al. | Morphology transcription with TiO2 using chemical solution growth and its application for photocatalysts | |
| CN101635320A (en) | Method for manufacturing titanium dioxide mesoporous film ultraviolet photoelectric detection prototype device | |
| JP2004277260A (en) | Porous ceramic material and method of manufacturing the same | |
| CN103361655B (en) | Method for preparing super-hydrophobicity surface on metallic aluminium | |
| CN1786264A (en) | Method of low temperature preparing C axle preferrel orientation titanium dioxide film | |
| Tadanaga | Preparation and application of alumina-and titania-nanocrystals-dispersed thin films via sol-gel process with hot water treatment | |
| Takeuchi et al. | Preparation of crystalline TiO2 thin film photocatalysts on polycarbonate substrates by a RF-magnetron sputtering deposition method | |
| Uchiyama et al. | Preparation of metal oxide thin films from organic-additive-free aqueous solutions by low-speed dip-coating | |
| Nebi et al. | Effect of heat treatment on the structural properties of TiO2 films produced by sol-gel spin coating technique | |
| CN104086092A (en) | Super-hydrophilic self-cleaning antifogging composite film, and preparation method and application thereof | |
| CN108218247B (en) | TiO with hierarchical structure morphology2Method for producing thin film | |
| CN109734327B (en) | Modified PTA method for preparing titanium dioxide super-hydrophilic self-cleaning photocatalytic film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |